Novel annularly-linked triazole compounds

ABSTRACT

Novel bicyclic triazole compounds of the formula I have an excellent herbicidal and plant-growth regulating action. The compounds correspond to the formula I    &lt;IMAGE&gt;  (I)  wherein Q is hydrogen or halogen, T is halogen, and Z is a radical -XR or -COXR, in which X is oxygen, sulfur or a radical -NR2-, R is hydrogen, a C1-C6-alkyl, C hd 3-C6-cycloalkyl, C hd 2-C6-alkenyl or C3-C6-alkynyl radical, which is unsubstituted or substituted by halogen, or is a radical -A-COXR1, in which A is a C1-C4-alkylene bridge and R1 is hydrogen or C1-C4-alkyl, C3-C6-cycloalkyl, C3-C4-alkenyl or C3-C4-alkynyl.

CROSS-REFERENCE TO RELATED APPLICATION

This is a continuation-in-part of our application Ser. No. 886,501,filed July 17, 1986, now U.S. Pat. No. 4,789,394.

The present invention relates to novel annularly-linked triazolecompounds of the formula I given below, which have an herbicidal actionand an action regulating plant growth, and to the production of thesenovel compounds. The invention relates also to compositions containingthe novel compounds, and to the use thereof for the selective control ofweeds or for the regulation of plant growth.

The novel annularly-linked triazole compounds correspond to the formulaI ##STR2## wherein

Q is hydrogen or halogen,

T is halogen, and

Z is a radical --XR or --COXR, in which

X is oxygen, sulfur or the radical --NR₁ --,

R is hydrogen, a C₁ -C₆ -alkyl, C₃ -C₆ -cycloalkyl, C₂ -C₆ -alkenyl orC₃ -C₆ -alkynyl radical, which is unsubstituted or substituted byhalogen, or is a radical --A--COXR₁, in which

A is a C₁ -C₄ -alkylene bridge and

R₁ is hydrogen or C₁ -C₄ -alkyl, C₃ -C₆ -cycloalkyl, C₃ -C₄ -alkenyl orC₃ -C₄ -alkynyl.

By halogen in the formula I is meant fluorine, chlorine, bromine oriodine. In the case of the substituent T, chlorine and bromine arepreferred.

The term `alkyl` on its own or as part of another substituent embracesboth branched-chain and straight-chain alkyl groups. Examples are:methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,tert-butyl, n-pentyl, isopentyl, neopentyl and also hexyl with theisomers thereof.

The alkenyl and alkynyl radicals can likewise be branched-chain orstraight-chain, and contain preferably 2-6 carbon atoms. Examples are:allyl, methallyl, butenyl, butadienyl, methylbutenyl, dimethylbutenyl,pentenyl, hexenyl, pentenedienyl and hexenedienyl, butyne, methylbutyne,pentyne, hexyne and dimethylbutyne.

The alkenyl bridge corresponding to the radical A can be straight-chainor branched-chain. It can be for example methylene, ethylene,1-methylmethylene, 1,1-dimethylethylene, 1- or 2-methylethylene,1,2-dimethylethylene, 1,1- or 2,2-dimethylethylene, propylene orbutylene.

The compounds of the formula I have an action regulating plant growth,and can be used for reducing vegetative growth.

The compounds of the formula I have however in particular herbicidalactivity, and are suitable for the control of weeds, especiallydicotyledonous weeds. It has been shown that with these compounds it ispossible to destroy otherwise very resistant problem weeds of the Galiumfamily: bedstraw plants, for example Galium verum, yellow galium, Galiumaparine, goose grass, Galium mollugo, common bedstraw, and so forth,against which other known herbicides are frequently inadequatelyeffective.

A great advantage in this respect is that the novel compounds of theformula I behave towards many cultivated plants, such as cereals, maize,rice and also rape-seed, in a selective manner, and can thus be employedfor controlling weeds in such crops.

The active substances of the formula I are as a rule successfullyapplied in amounts of 0.005 to 4 kg per hectare, especially 0.001 to 1kg per hectare.

In lower applied amounts, the compounds of the formula I aredistinguished by good selective growth-inhibiting and selectiveherbicidal properties, which render them excellently suitable for use incrops of cultivated plants, especially in crops of cereals, cotton,soya-bean, maize and rice. It is also possible in some cases to destroyweeds which could be dealt with hitherto only by the application oftotal herbicides.

The mode of action of these active substances is unusual. Many arecapable of being translocated, that is to say, they are taken up by theplants and transported to other locations, where they produce thedesired effect. It is thus possible for example by surface treatment ofperennial weeds to destroy them at the roots. The novel compounds of theformula I are effective in applied amounts which are very small comparedwith the amounts required to obtain the same effect using otherherbicides and plant-growth regulators.

9-Aryl-8,10-dioxo-4,1,7,9-thiatriazabicyclo[5.3.0]-decane-4,4-dioxidesare already known as being herbicides from the GermanOffenlegungsschrift No. 2,638,543.

It has now been found that, surprisingly,.the novel compounds of theformula I of the present invention have properties which areconsiderably better than those of the prior known compounds. With thenovel compounds of the formula I, the amount of active substance perhectare can be drastically reduced, a factor which is of advantage bothecologically and economically.

Novel annularly-linked 1-phenyl-2,5-dioxo-1H-1,3,4-triazole compounds ofthe formula I exhibiting a good action are those wherein

Q is hydrogen or fluorine,

T is fluorine, chlorine or bromine, and

Z has the meaning defined under the formula I;

particularly the compounds in which

Q is hydrogen or fluorine,

T is chlorine or bromine,

Z is a radical --XR or --COXR,

X is oxygen, sulfur or the radical --NR₁ --,

R is hydrogen, C₁ -C₄ -alkyl, C₃ -C₆ -cycloalkyl, C₃ -C₆ -alkenyl or C₃-C₆ -alkynyl, and

R₁ is hydrogen or C₁ -C₄ -alkyl, C₃ -C₆ -cycloalkyl, C₃ -C₄ -alkenyl orC₃ -C₄ -alkynyl

A good action is exhibited likewise by the compounds formula I in which

Q is hydrogen or fluorine,

T is chlorine or bromine,

Z is a radical --XR,

X is oxygen or sulfur,

R is hydrogen, a , C₁₃ -C₆ -alkyl,C₃ -C₆ -cycloalkyl, C₃ -C₆ -alkenyl orC₃ -C₆ -alkynyl radical, which is unsubstituted or substituted byhalogen;

also by those compounds in which

Q is hydrogen or fluorine,

T is chlorine or bromine,

Z is a radical --XR,

X is a radical --NR₁ --,

R is hydrogen, C₁ -C₆ -alkyl, C₃ -C₆ -cycloalkyl, C₃ -C₆ -alkenyl or C₃-C₆ -alkynyl, and

R₁ is hydrogen, C₁ -C₄ -alkyl, C₃ -C₆ -cycloalkyl, C₃ -C₄ -alkenyl or C₃-C₄ -alkynyl.

A good action is exhibited also by the compounds of the formula Iwherein

Q is hydrogen or fluorine,

T is chlorine or bromine,

Z is a radical --COXR,

X is oxygen or sulfur,

R is hydrogen, C₁ -C₆ -alkyl, C₃ -C₆ -cycloalkyl, C₃ -C₆ -alkenyl or C₃-C₆ -alkynyl;

and moreover by those compounds of the formula I in which

T is chlorine or bromine,

Q is hydrogen or fluorine,

Z is a radical --XR,

R is a radical --A--COXR₁,

A is a C₁ -C₄ -alkylene chain,

X is oxygen or sulfur, and

R₁ is hydrogen, C₁ -C₆ -alkyl, C₃ -C₆ -cycloalkyl, C₃ -C₆ -alkenyl or C₃-C₆ -alkynyl;

particularly the compound:

9-(2-fluoro-4-chloro-5-isopropyloxy-phenyl)-8,10-dioxo-4,1,7,9-thiatriabicyclo[5.3.0]-decane-4,4-dioxide.

The compounds of the formula I are produced by reacting a1-(2-phenyl)-1H-1,3,4-triazolidine-2,5-dione of the formula II ##STR3##wherein Q, T and Z have the meanings defined under the formula I, in aninert organic solvent at a temperature of 0° to 150° C., in the presenceof an amount of base as catalyst, with divinylsulfone (CH₂ ═CH)SO₂.

This condensation or addition reaction is best performed in a polaraprotic organic solvent, in the presence of a base as catalyst.Reference is made in this respect to G. Zinner Arch. Pharm. 299 (1966),pp. 312-314, wherein the production of9-phenyl-8,10-dioxo-4,1,7,9-thiatriazabicyclo[5.3.0]decane-4,4-dioxideis described; or to the German Auslegeschrift No. 2,638,543, in whichthe production of 9-aryl-8,10-dioxo- or-8-one-10-thione-4,1,7,9-thiatriazabicyclo[5.3.0]decane-4,4-dioxides isdescribed in general.

Polar aprotic organic solvents suitable for this condensation reactionare for example: formamides, aralkylsulfoxides, cyclic ketones, loweralkanols or nitriles.

This condensation or addition reaction is catalysed by the addition ofan amount of base, such as alkanolic KOH or NaOH. The temperature forthe reaction can vary between 0° and 150° C.

The starting materials of the formula II are for the most part novel.The production of 2-phenyl-1,2,4-triazolidine- 3,5-dione, termed also4-phenylurazole or N-phenylimide of azodicarboxylic acid, has alreadybeen described by J. Thiele, et al., Ann. 283 (1984), p. 1. Furtherreferences in this connection are J. Stolle Ber. 45 (1912), p. 273, G.Zinner, et al., Arch. Pharm. 294 (1961), pp. 370-372, and also R.C.Cockson, et al., Tetrahedron Letters 14 (1962), pp. 615-618. The processcomprises for example cyclising a1-ethoxycarbonyl-4-(phenyl)-semicarbazide, C₂ H₅-O-CO-NH-NH-CO-NH-phenyl, correspondingly substituted in the phenylnucleus, in a hot alkaline medium; and isolating the4-(2-phenyl)-1,2,4-triazolidine-3,5-dione from an acid medium, fromwhich it precipitates in crystalline form.

The semicarbazides required for the production of the1,3,4-triazole-2,5-dione of the formula II and which correspond to theformula III ##STR4## wherein R₂ is a C₁ -C₆ -alkyl or benzyl radical,and Q, T and Z have the meanings defined under the formula I, can beobtained by reaction of hydrazine hydrate with the equimolar amount of adialkyl carbonate, and reaction of the formed alkyl carbazate with theequimolar amount of a phenylisocyanate.

The production of the novel annularly-linked triazole compounds of theformula I can be illustrated by the following reaction diagram: ##STR5##

The compounds of the formula I, according to the meaning of Z, can beconverted into one another. An important part in this respect is playedby the3-aminoanilidene,9-(3-amino-4-halophenyl)-8,10-dioxo-4,1,7,9-thiatriazabicyclo[5.3.0]decane-4,4-dioxidesof the formula Ia. They are obtained by treating a9-(4-halophenyl)-8,10-dioxo-4,1,7,9-thiatriazabicyclo[5.3.0]-decane-4,4-dioxidewith 1 to 1.5 molar equivalents of a nitrating agent, for example fumingnitric acid, or with a mixture of fuming nitric acid and sulfuric acid.The solvent used for the purpose can be concentrated sulfuric acid, andthe reaction temperature is to be maintained between -5° and +5° C. The3-nitroanilide,9-(3-nitro-4-halophenyl)-8,10-dioxo-4,1,7,9-thiatriazabicyclo[5.3.0]-decane-4,4-dioxideobtained is subsequently reduced to the amine, for example in an inertorganic solvent with hydrogen under normal pressure in the presence ofRaney nickel, or in water, acetic acid, ethanol or ethyl acetate with2.5 to 10 molar equivalents of iron filings with at least the equimolaramount of glacial acetic acid at a temperature of 50°-100° C.

These reactions can be illustrated by the following reaction schemes:##STR6##

In these formulae, Q and T have the meanings defined under the formulaI. The inventive 3-aminoacetanilides of the formula Ia are important keyproducts for the production of further compounds of the formula I. Theyand the 3-nitroanilides of the formula IV are likewise subject matter ofthe present invention.

The 3-aminoanilides of the formula Ia can be converted into furthercompounds of the formula I; for example by treatment with an alkylatingagent, such as an alkyl halide or an alkylsulfonic or -arylsulfonicacid, there are obtained the compounds of the formula I in which Z isthe amino radical --N(R)R₁.

Furthermore, the 3-aminoanilides of the formula Ia can be converted inan excess of a mineral acid (for example hydrochloric acid or sulfuricacid) with 1-15 molar equivalents of sodium nitrite into the diazoniumsalt, which is then converted, by decomposition in water or acetic acid,with copper cyanate into the 3-cyanoanilide,9-(3-cyano-4-halophenyl)-8,10-dioxo-4,1,7,9-thiatriazabicyclo[5.3.0]decane-4,4-dioxideof the formula VI, which for its part is hydrolysed, by boiling withwater and the catalytic amount of a base, to the 3-carboxyanilide,9-(3-carboxy-4-halophenyl)-8,10-dioxo-4,1,7,9-thiatriazabicyclo[5.3.0]decane-4,4-dioneof the formula VI. By reaction of this carboxylic ester with a stronghalogenating agent, such as phosphorus oxychloride, phosphorusoxybromide, thionyl chloride, thionyl bromide, sulfuryl chloride orbromo succinimide, these is obtained the acid halide of the formula VII,which can be converted, by reaction with an alkanol or thiol of theformula HXR, into a compound of the formula I in which Z is the carbonicacid radical --COXR. These reactions can be illustrated by the followingreaction diagram: ##STR7##

In these formulae, Q, R, T and X have the meanings defined under theformula I.

The diazonium salt produced by reaction of the 3-aminoanilide of theformula Ia with sodium nitrite can be either hydrolysed to the phenol,or converted into a thiophenol or thiophenol derivative, and thesederivatives in their turn can be etherified again according to thefollowing reaction diagram: ##STR8##

In these formulae, A, Q, R, R₁ and T have the meanings defined under theformula I.

The compounds of the formula I have herbicidal properties and alsoproperties enabling plant growth to be greatly reduced. Bothmonocotyledons and dicotyledons are impaired in their growth.

Thus, for example, the leguminosae frequently planted as cover crops inagriculture in tropical regions can be selectively inhibited in theirgrowth by the compounds of the formula I, the result being that soilerosion between the cultivated plants is prevented, without the covercrops being able to compete with the main cultivated crop.

A reduction of the vegetative growth enables in the case of manycultivated plants the growth density to be increased, so that higheryields for the same area of land can be achieved.

An additional factor contributing to the increase in yield with the useof growth inhibitors is that the formation of blossom and fruit benefitsto a greater extent from the nutritive substances, because thevegetative growth is restricted.

The desiccating and defoliation action of these compounds is used inpotato and cotton crops, shortly before they are gathered, in order torender harvesting easier by dessicating undesirable vegetative plantparts.

The compounds of the formula I have however in particular herbicidalactivity, and are suitable for the control of weeds, especiallydicotyledonous weeds. It has been shown that with these compounds it ispossible to destroy otherwise very resistant problem weeds of the Galiumfamily: bedstraw plants, for example Galium verum, yellow galium, Galiumaparine, goose grass, Galium mollugo, common bedstraw, and so forth,against which other known herbicides are frequently inadequatelyeffective.

A great advantage in this respect is that the novel compounds of theformula I behave towards many cultivated plants, such as cereals, maize,rice and also rape-seed, in a selective manner, and can thus be employedfor controlling weeds in such crops.

The active substances of the formula I are as a rule successfullyapplied in amounts of 0.005 to 4 kg per hectare, especially 0.001 to 1kg per hectare.

In lower applied amounts, the compounds of-the formula I aredistinguished by good selective growth-inhibiting and selectiveherbicidal properties, which render them excellently suitable for use incrops of cultivated plants, especially in crops of cereals, cotton,soya-bean, maize and rice. It is also possible in some cases to destroyweeds which could be dealt with hitherto only by the application oftotal herbicides.

The mode of action of these active substances is unusual. Many arecapable of being translocated, that is to say, they are taken up by theplant and transported to other locations, where they produce the desiredeffect. It is thus possible for example by surface treatment ofperennial weeds to destroy them at their roots. The novel compounds ofthe formula I are effective in applied amounts which are very smallcompared with the amounts required to obtain the same effect using otherherbicides and plant-growth regulators.

With larger applied amounts of active substance, all the tested plantsare impaired in their development to the extent that they wither.

The present invention relates also to herbicidal andplant-growth-regulating compositions containing a novel activeingredient of the formula I, and also to processes for the pre- andpost-emergence controlling of weeds, and for the reduction of growth ofmonocoteledonous and dicotyledonous plants, tropical cover crops andside shoots of tobacco plants.

The compounds of the formula I are used either in an unmodified form orpreferably in compositions, together with auxiliaries customarilyemployed in formulation practice, and are thus processed, in a knownmanner, for example into the form of emulsion concentrates, directlysprayable or dilutable solutions, diluted emulsions, wettable powders,soluble powders, dusts or granulates, and also encapsulations in forexample polymeric substances. The application processes, such asspraying, atomising, dusting, scattering or pouring, and likewise thetype of compositions, are selected to suit the objectives to be achievedand the given conditions.

The formulations, that is to say, the compositions or preparationscontaining the active ingredient of the formula I and optionally a solidor liquid additive, are produced in a known manner, for example by theintimate mixing and/or grinding of the active ingredients withextenders, such as with solvents, solid carriers and optionallysurface-active compounds (tensides).

Suitable solvents are: aromatic hydrocarbons, preferably the fractionsC₈ to C₁₂, such as xylene mixtures or substituted naphthalenes, phthalicesters, such as dibutylor dioctylphthalate, aliphatic hydrocarbons, suchas cyclohexane or paraffins, alcohols and glycols, as well as ethers andesters thereof, such as ethanol, ethylene glycol, ethylene glycolmonomethyl or -ethyl ethers, ketones, such as cyclohexanone, stronglypolar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide ordimethylformamide, as well as optionally epoxidised vegetable oils, suchas epoxidised coconut oil or soyabean oil; or water.

The solid carriers used, for example for dusts and dispersible powders,are as a rule natural mineral fillers, such as calcite, talcum, kaolin,montmorillonite or attapulgite. In order to improve the physicalproperties, it is also possible to add highly dispersed silicic acid orhighly dispersed absorbent polymers. Suitable granulated adsorptivecarriers are porous types, for example pumice, ground brick, sepioliteor bentonite, and suitable nonsorbent carriers are materials such ascalcite or sand. There can also be used a great number of pre-granulatedmaterials of inorganic or organic nature, such as in particular dolomiteor ground plant residues.

Suitable surface-active compounds are, depending on the nature of theactive substance of the formula I to be formulated, nonionic, cationicand/or anionic tensides having good emulsifying, dispersing and wettingproperties. By `tensides` are also meant mixtures of tensides.

Suitable anionic tensides are both so-called water-soluble soaps as wellas water-soluble, synthetic, surface-active compounds.

Soaps which are applicable are the alkali metal, alkaline-earth metal oroptionally substituted ammonium salts of higher fatty acids (C₁₀ -C₂₂),for example the Na or K salts of oleic or stearic acid, or of naturalfatty acid mixtures, which can be obtained for example from coconut oilor tallow oil. Also to be mentioned are the fatty acid-methyl-taurinesalts.

So-called synthetic tensides are however more frequently used,particularly fatty sulfonates, fatty sulfates, sulfonated benzimidazolederivatives or alkylarylsulfonates. The fatty sulfonates or sulfates areas a rule in the form of alkali metal, alkaline-earth metal oroptionally substituted ammonium salts, and contain an alkyl group having8 to 22 C atoms, `alkyl` including also the alkyl moiety of acyl groups,for example the Na or Ca salts of ligninsulfonic acid, ofdodecylsulfuric acid ester or of a fatty alcohol sulfate mixtureproduced from natural fatty acids. Included among these are also thesalts of sulfuric acid esters and sulfonic acids of fatty alcoholethylene oxide adducts. The sulfonated benzimidazole derivativespreferably contain 2 sulfonic acid groups and a fatty acid group having8-22 C atoms. Alkylarylsulfonates are for example the Na, Ca ortriethanolamine salts of dodecylbenzenesulfonic acid, ofdibutylnaphthalenesulfonic acid or of a naphthalenesulfonicacid-formaldehyde condensation product. Also suitable are correspondingphosphates, for example salts of the phosphoric ester of ap-nonylphenol-(4-14)-ethylene oxide adduct, and phospholipides.

Suitable nonionic tensides are in particular polyglycol etherderivatives of aliphatic or cycloaliphatic alcohols, saturated orunsaturated fatty acids and alkylphenols, which contain 3 to 30 glycolether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbonradical and 6 to 18 carbon atoms in the alkyl moiety of thealkylphenols.

Further suitable nonionic tensides are the water-soluble polyethyleneoxide adducts, which contain 20 to 250 ethylene glycol ether groups and10 to 100 propylene glycol ether groups, with polypropylene glycol,ethylenediaminopolypropylene glycol and alkylpolypropylene glycol having1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usuallycontain 1 to 5 ethylene glycol units per propylene glycol unit. Examplesof nonionic tensides which may be mentioned are:nonylphenolpolyethoxyethanol, castor oil polyglycol ethers,polypropylene/polyethyleneoxy adducts, tributylphenoxypolyethoxyethanol,polyethylene glycol and octylphenoxypolyethoxyethanol. Suitable also arefatty acid esters of polyoxyethylenesorbitan, such aspolyoxyethylenesorbitan-trioleate.

In the case of the cationic tensides, they are in particular quaternaryammonium salts which contain as N-substituents at least one alkyl grouphaving 8 to 22 C atoms and, as further substituents, lower, optionallyhalogenated alkyl, benzyl or lower hydroxyalkyl groups. The salts arepreferably in the form of halides, methyl sulfates or ethyl sulfates,for example stearyltrimethylammonium chloride orbenzyldi(2-chloroethyl)ethylammonium bromide.

The tensides customarily used in formulation practice are described,inter alia, in the following publications:

"Mc Cutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp.,Ridgewood, N.J., 1979; and

Dr. Helmut Stache, "Tenside Taschenbuch", Carl Hanser Verlag,Munich/Vienna, 1981.

The herbicidal preparations contain as a rule 0.1 to 95%, especially 0.1to 80%, of active ingredient of the formula I, 1 to 99.9% of a solid orliquid additive, and 0 to 25%, particularly 0.1 to 25%, of a tenside.

Preferred formulations are made up in particular as follows: (% =percent by weight):

Emulsifiable concentrates

active ingredient of the formula I: 1 to 20%, preferably 5 to 10%

surface-active agent: 5 to 30%, preferably 10 to 20%

liquid carrier: 50 to 94%, preferably 70 to 85% .

Dusts

active ingredient of the formula I: 0.1 to 10%, preferably 0.1 to 1%

solid carrier: 99.9 to 90%, preferably 99.9 to 99% .

Suspension concentrates

active ingredient of the formula I: 5 to 75%, preferably 10 to 50%

water: 94 to 25%, preferably 90 to 30%

surface-active agent, 1 to 40%, preferably 2 to 30% .

Wettable powders

active ingredient of the formula I: 0.5 to 90%, preferably 1 to 80%

surface-active agent: 0.5 to 20%, preferably 1 to 15%

solid carrier: 5 to 95%, preferably 15 to 90% .

Granulates

active-ingredient of the formula I: 0.5 to 30%, preferably 3 to 15%

solid carrier: 99.5 to 70%, preferably 97 to 85% .

Whereas commercial products are preferably in the form of concentratedcompositions, the preparations employed by the end-user are as a rulediluted. The preparations can on application be diluted down to 0.001%of active ingredient. The applied amounts are usually 0.005 to 5 kg ofactive substance per hectare.

The compositions can also contain further additives, such asstabilisers, antifoaming agents, viscosity regulators, binders andadhesives, as well as fertilisers or other active substances forobtaining special effects.

The following Examples illustrate the production of some compounds ofthe formula I. Further active substances obtained in a correspondingmanner are listed in the Tables subsequently given. Temperatures aregiven in degrees Centigrade and pressure values are in millibars.

EXAMPLE 1 Production of9-(2-fluoro-4-chloro-5-isopropyloxyphenyl)8,10-dioxo-4,1,7,9-thiatriazabicyclo[5.3.0]decane-4,4-dioxide##STR9##

A solution of 45.0 g (0.195 mol) of2-fluoro-4-chloro-5-isopropyloxy-phenylisocyanate in 50 ml of toluene isadded dropwise at 10° C. to a solution of 20.5 g (0.195 mol) ofhydrazinecarboxylic acid ethyl ester in 200 ml of toluene. After onehour, the formed precipitate is filtered off, and this is treated with250 ml of 4 N sodium hydroxide solution. The temperature is raised to60° C. and a clear yellow solution is obtained. On acidifying this to pH1 with concentrated hydrochloric acid, a white precipitate is formed.After one hour's stirring at 60° C., filtration is performed and theresidue is dried over phosphorus pentoxide. The yield is 52.5 g (93.9%of theory) of 4-(2-fluoro-4-chloro-5-isopropyloxyphenyl)-urazole havinga melting point of 193°-194° C.

17.5 g (0.061 mol) of the above urazole are dissolved in 300 ml ofethanol. After the addition of 7.2 g (0.061 mol) of divinyl sulfone and0.5 ml of a 6 N sodium hydroxide solution, the reaction mixture isrefluxed for 8 hours, the product commencing to precipitate after about1 hour. The yield is thus 23.0 g (92.7% of theory) of9-(2-fluoro-4-chloro-5-isopropyloxy-phenyl-8,10-dioxo-4,1,7,9-thiatriazabicyclo[5.3.0]decane-4,4-dioxidehaving a melting point of 195°-196° C.

EXAMPLE 2 Production of9-(2-fluoro-4-chloro-4-difluoromethoxyphenyl)8,10-dioxo-4,1,7,9-thiatriazabicyclo[5.3.0]decane-4,4-dioxide##STR10##

To a mixture, heated to 50° C., of 5.75 g (0.02 mol) of4-(2-fluoro-4-chloro-5-difluoromethoxyurazole and 100 ml of ethanol areadded 4 drops of 6 N KOH and 2.36 g (0.02 mol) of divinyl sulfone.Stirring is maintained until everything has gone into solution, and thesolution is then refluxed for 8 hours. After it has cooled, thesubstance which has precipitated is filtered off with suction and driedin vacuo. The yield is 6.9 g of9-(2-fluoro-4-chloro-5-difluoromethoxyphenyl)-8,10-dioxo-4,1,7,9-thiatriazabicyclo[5.3.0]decane-4,4-dioxide,which has a melting point of 195°-196° C.

EXAMPLE 3 Production of9-(2-fluoro-4-chloro-5-aminophenyl)-8,10-dioxo-4,1,7,9-thiadiazabicyclo[5.3.0]decane-4,4-dioxide##STR11##

Hydrogen is introduced into a mixture of 15 g of9-(2-fluoro-4-chloro-5-nitrophenyl)-8,10-dioxo-4,1,7,9-thiadiazabicyclo[5.3.0]decane-4,4-dioxide,3 g of Raney nickel, 300 ml of tetrahydrofuran and 150 ml ofdimethylformamide at 20°-25° C. and under normal pressure until thestoichiometric amount has been absorbed. After completion of thereaction, the catalyst is filtered off, and the filtrate is concentratedin vacuo. The residue consists of 11.6 g of9-(2-fluoro-4-chloro-5-aminophenyl)-8,10-dioxo-4,1,7,9-thiadiazabicyclo[5.3.0]decane-4,4-dioxidehaving a melting point of 219°-220° C.

The9-(2-fluoro-4-chloro-5-nitrophenyl)-8,10-dioxo-4,1,7,9-thiadiazabicyclo[5.3.0]decane-4,4-dioxiderequired as starting material is obtained as follows:

a) 19.1 g of9-(2-fluoro-4-chlorophenyl)-8,10-dioxo-4,1,7,9-thiatriazabicyclo[5.3.0]decane-4,4-dioxideare added in small portions to 125 ml of concentrated sulfuric acid,which is being stirred at 0° C. To this solution are then added dropwiseat 0° C., with stirring, 2.5 ml of fuming nitric acid. After beingstirred for one hour at room temperature, the reaction mixture is pouredonto ice, and the substance which precipitates is filtered off undersuction. It is washed with water and dried to thus yield 18 g of9-(2-fluoro-4-chloro-5-nitrophenyl)-8,10-dioxo-4,1,7,9-thiatriazabicyclo-[5.3.0]decane-4,4-dioxidehaving a melting point of 251°-252° C.

EXAMPLE 4 Production of9-(2-fluoro-4-chloro-5-hydroxycarbonylmethylthiophenyl)-8,10-dioxo-4,1,7,9-thiatriazabicyclo-[5.3.0]decanedione##STR12##

To a mixture of 17 g (0.047 mol) of9-(5-amino-2-fluoro-4-chlorophenyl)-8,10-dione-4,1,7,9-thiatriazabicyclo[5.3.0]-decanedione(Example 3) in 25 ml of conc. hydrochloric acid and 130 ml of water,there is added slowly at a temperature of 0°-5° C., with slow stirring,under the surface, a solution of 3.9 g (0.0565 mol) of sodium nitrite in15 ml of water. After everything has been added, stirring is continuedfor half an hour at this temperature; then there is added aminosulfonicacid (H₂ NSO₃ H) in order to bind the excess nitrite and subsequently amixture of 5.5 g of thioglycolic acid (0.06 mol) and 3.1 g of basiccopper carbonate (2 CuCO₃.Cu(OH₂) in 50 ml of water. The mixture isstirred for two hours at room temperature. The mixture is then extractedwith ethyl acetate. The extracts are washed with water and saturatedsalt solution dried, and concentrated by evaporation. The residue thusyields 11.6 g of the title product.

The compounds listed in the following Tables are produced in a mannercorresponding to that of these Examples.

                  TABLE 1                                                         ______________________________________                                         ##STR13##                                                                    No.    Q     T       Z                                                        ______________________________________                                        1001   F     Cl      OCH(CH.sub.3).sub.2                                                                         m.p. 195-196°                       1002   F     Cl      OCH.sub.3     m.p. 212-214°                       1003   F     Cl      OC.sub.2 H.sub.5                                         1004   F     Cl      OC.sub.3 H.sub.7 n                                       1005   F     Cl      OC.sub.4 H.sub.9 n                                       1006   F     Cl      OCH.sub.2 CH(CH.sub.3).sub.2                             1007   F     Cl      OCH(CH.sub.3)C.sub.2 H.sub.5                             1008   F     Cl      OC(CH.sub.3).sub.3                                       1009   F     Br      OCH(CH.sub.3).sub.2                                      1010   F     Br      OCH.sub.3                                                1011   F     Cl      OCH.sub.2 CHCH.sub.2                                     1012   F     Cl      OCH.sub.2 C(CH.sub.3)CH.sub. 2                           1013   F     Cl      OCH.sub.2 CCH m.p. 224-226°                       1014   H     Cl      OC.sub.3 H.sub.7 n                                       1015   H     Br      OC.sub.4 H.sub.9 n                                       1016   F     Cl      OH            m.p. >300°                          1017   F     Cl      SCH.sub.3                                                1018   F     Cl      SC.sub.2 H.sub.5                                         1019   F     Cl      SCH(CH.sub.3).sub.2                                      1020   F     Cl      SC.sub.3 H.sub.7 n                                       1021   F     Cl      SC.sub.4 H.sub.9 n                                       1022   F     Cl      SH                                                       1023   F     Cl      N(CH.sub.3).sub.2                                        1024   F     Cl      NHCH.sub.3                                               1025   F     Cl      N(CH.sub.3)CH(CH.sub.3).sub.2                            1026   F     Br      N(CH.sub.3).sub.2                                        1027   F     Cl      NH.sub.2                                                 1028   H     Cl      COOCH(CH.sub.3).sub.2                                    1029   H     Cl      COOC.sub.3 H.sub.7 n                                     1030   H     Cl      COOCH.sub.3                                              1031   H     Cl      COOC.sub.2 H.sub.5                                       1032   H     Cl      COSCH.sub.3                                              1033   H     Cl      COSC.sub.2 H.sub.5                                       1034   H     Cl      COSC.sub.3 H.sub.7 n                                     1035   H     Br      COOCH(CH.sub.3).sub.2                                    1036   H     Br      COOC.sub.3 H.sub.7 n                                     1037   F     Br      COSC.sub.2 H.sub.5                                       1038   H     Cl      COOCH.sub.2 CHCH.sub.2                                   1039   F     Br      COOCH.sub.2 CH CH.sub.2                                  1040   F     Cl      COOCH(CH.sub.3).sub.2                                    1041   F     F       COOCH(CH.sub.3).sub.2                                    1042   F     Cl      COOCH.sub.3                                              1043   F     Cl      COOC.sub.2 H.sub.5                                       1044   F     Cl      COOC.sub.3 H.sub.7 n                                     1045   F     Cl      COSCH.sub.3                                              1046   F     Cl      COSC.sub.2 H.sub.5                                       1047   F     Cl      COSC.sub.3 H.sub.7 n                                     1048   F     Cl      COSCH(CH.sub.3).sub.2                                    1049   F     Cl      COSC.sub.4 H.sub.9 n                                     1050   F     F       COOCH.sub.3                                              1051   F     Br      COOCH(CH.sub.3).sub.2                                                                       m.p. >212°                          1052   F     Br      COOCH.sub.3   m.p. 208-210°                       1053   F     Br      COOH          m.p. >250°                          ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                         ##STR14##                                                                    No.     Q     T        Z                                                      ______________________________________                                        2.001   F     Cl       OCHF.sub.2  m.p. 232-234°                       2.002   F     Cl       OCF.sub.2 CHClF                                        2.003   F     Cl       OCH.sub.2 CClCH.sub.2                                                                     m.p. 160-161°                       2.004   F     Cl       OCF.sub.3                                              2.005   F     Cl       SCF.sub.3                                              2.006   F     Cl       SCHF.sub.2                                             2.007   F     Cl       OCF.sub.2 CHF.sub.2                                                                       m.p. 225-227°                       2.008   F     Cl       OCClCHCl    m.p. 187-190°                       2.009   F     Cl       OCH.sub.2CI                                            2.010   F     Cl       OCH.sub.2 CClCHCl                                      2.011   F     Cl       OCH(CH.sub.3)CH.sub.2 Cl                               2.012   F     Cl       OCH.sub.2 CH.sub.2 F                                   2.013   F     Cl       OCH.sub.2 CH.sub.2 Cl                                  2.014   F     Cl       OCH.sub.2 CH.sub.2 Br                                  2.015   F     Cl       OCH.sub.2 CH.sub.2 I                                   2.016   F     Cl       OCF.sub.2 CHFCF.sub.3                                                                     m.p. 144-147°                       2.017   F     Cl       OCF.sub.2 CHCl.sub.2                                   2.018   F     Cl       OCF.sub.2 CF.sub.3                                                                        m.p. 205-207°                       2.019   F     Cl       OCClF.sub.2                                            2.020   H     Br       OCF.sub.3                                              2.021   H     Cl       OCHF.sub.2                                             2.022   H     Cl       OCH.sub.2 CClCH.sub.2                                  2.023   H     Br       OCHCClCH.sub.2                                         2.024   H     Cl       OCF.sub.2 CF.sub.3                                     2.025   H     Br       OCF.sub.2 CF.sub.3                                     2.026   H     Cl       SCF.sub.3                                              2.027   H     Br       SCF.sub.3                                              2.028   H     Cl       OCH(CH.sub.3)CH.sub.2 Cl                               2.029   H     Br       OCH(CH.sub.3)CH.sub.2 Cl                               2.030   H     Cl       OCH(CH.sub.3)CH.sub.2 Cl                               ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                         ##STR15##                                                                    No.     Q     T       Z                                                       ______________________________________                                        3.001   F     Cl      COOCH.sub.2 COOCH.sub.3                                 3.002   F     Cl      COOCH.sub.2 COOC.sub.2 H.sub.5                          3.003   F     Cl      COOCH.sub.2 COOCH(CH.sub.3).sub.2                       3.004   F     Cl      COOCH(CH.sub.3)COOCH.sub.3                              3.005   F     Cl      COOCH(CH.sub.3)COOC.sub.2 H.sub.5                       3.006   F     Cl      COOCH(CH.sub.3)COOC.sub.3 H.sub.7 -n                    3.007   F     Cl      COOCH(CH.sub.3)COOCH(CH.sub.3).sub.2                    3.008   F     Cl      COOCH(CH.sub.3)COOC.sub.4 H.sub.9 -n                    3.009   F     Cl      COOCH(CH.sub.3)COOCH.sub.2 CH(CH.sub.3).sub.2           3.010   F     Cl      COOCH(CH.sub.3)COOCH(CH.sub.3)C.sub.2 H.sub.5           3.011   F     Cl      COSCH.sub.2 COOCH.sub.3                                 3.012   F     Cl      COSCH.sub.2 COOC.sub.2 H.sub.5                          3.013   F     Cl      COSCH.sub.2 COOC.sub.3 H.sub.7 -n                       3.014   F     Cl      COSCH.sub.2 COOCH(CH.sub.3).sub.2                       3.015   F     Cl      COSCH.sub.2 COOCH.sub.2 CHCH.sub.2                      3.016   F     Cl      COSCH.sub.2 COOcyclohexyl                               3.017   F     Cl      COSCH.sub.2 COOC.sub.4 H.sub.9 -n                       3.018   F     Cl      COSCH(CH.sub.3)COOCH.sub.3                              3.019   F     Cl      COSCH(CH.sub.3)COOC.sub.2 H.sub.5                       3.020   F     Cl      COSCH(CH.sub.3)COOC.sub.3 H.sub.7 -n                    3.021   F     Cl      COSCH(CH.sub.3)COOCH(CH.sub.3).sub.2                    3.022   F     Cl      COSCH(CH.sub.3)COOC.sub.4 H.sub.9 -n                    3.023   F     Cl      COSCH(CH.sub.3)COOCH.sub.2 CH(CH.sub.3).sub.2           3.024   F     Cl      COSCH(CH.sub.3)COOCH(CH.sub.3)C.sub.2 H.sub.5           3.025   F     Cl      COSCH(CH.sub.3)COOC(CH.sub.3).sub.2                     3.026   F     Cl      COSCH(CH.sub.3)COOCH.sub.2 CHCH.sub.2                   3.027   F     Cl      COSCH(CH.sub.3)COOCHCCH                                 3.028   F     Cl      COSCH(CH.sub.3)COOcyclohexyl                            3.029   H     Cl      COOCH.sub.2 COOCH.sub.3                                 3.030   H     Cl      COOCH.sub.2 COOC.sub.2 H.sub.5                          3.031   H     Cl      COOCH.sub.2 COOC.sub.3 H.sub.7 -n                       3.032   H     Cl      COOCH.sub.2 COOCH(CH.sub.3).sub.2                       3.033   H     Cl      COOCH(CH.sub.3)COOCH.sub.3                              3.034   H     Cl      COOCH(CH.sub.3)COOC.sub.2 H.sub.5                       3.035   H     Cl      COOCH(CH.sub.3)COOC.sub.3 H.sub.7 -n                    3.036   H     Cl      COOCH(CH.sub.3)COOCH(CH.sub.3).sub.2                    3.037   H     Cl      COOCH(CH.sub.3)COOC.sub.4 H.sub.9 -n                    3.038   H     Cl      COOCH(CH.sub.3)COOCH.sub.2 CH(CH.sub.3).sub.2           3.039   H     Cl      COOCH(CH.sub.3)COOCH(CH.sub.3)C.sub.2 H.sub.5           3.040   H     Cl      COOCH(CH.sub.3)COOC(CH.sub.3).sub.2                     3.041   H     Cl      COSCH.sub.2 COOCH.sub.3                                 3.042   H     Cl      COSCH.sub.2 COOC.sub.2 H.sub.5                          3.043   H     Cl      COSCH.sub.2 COOC.sub.3 H.sub.7 -n                       3.044   H     Cl      COSCH.sub.2 COOCH(CH.sub.3).sub.2                       3.045   H     Cl      COSCH.sub.2 COOCH.sub.2 CHCH.sub.2                      3.046   H     Cl      COSCH.sub.2 COOcyclohexyl                               3.047   H     Cl      COSCH.sub.2 COOC.sub.4 H.sub.9 -n                       3.048   H     Cl      COSCH(CH.sub.3)COOCH.sub.3                              3.049   H     Cl      COSCH(CH.sub.3)COOC.sub.2 H.sub.5                       3.050   H     Cl      COSCH(CH.sub.3)COOC.sub.3 H.sub.7 -n                    3.051   H     Cl      COSCH(CH.sub.3)COOCH(CH.sub.3).sub.2                    3.052   H     Cl      COSCH(CH.sub.3)COOC.sub.4 H.sub.9 -n                    3.053   H     Cl      COSCH(CH.sub.3)COOCH.sub.2 CH(CH.sub.3).sub.2           3.054   H     Cl      COSCH(CH.sub.3)COOCH(CH.sub.3)C.sub.2 H.sub. 5          3.055   H     Cl      COSCH(CH.sub.3)COOC(CH.sub.3).sub.2                     3.056   H     Cl      COSCH(CH.sub.3)COOCH.sub.2 CHCH.sub.2                   3.057   H     Cl      COSCH(CH.sub.3)COOCH.sub.2 CCH                          3.058   H     Cl      COSCH(CH.sub.3)COOcyclohexyl                            3.059   F     Br      COOCH.sub.2 COOCH.sub.3                                 3.060   F     Br      COOCH.sub.2 COOC.sub.2 H.sub.5                          3.061   F     Br      COOCH(CH.sub.3)COOCH.sub.3                              3.062   F     Br      COOCH(CH.sub.3)COOCH(CH.sub.3).sub.2                    3.063   F     Br      COOCH(CH.sub.3)COOC.sub.2 H.sub.5                       3.064   F     Br      COOCH(CH.sub.3)COOCH.sub.2 CHCH.sub.2                   3.065   F     Br      COSCH.sub.2 COOCH.sub.3                                 3.066   F     Br      COSCH(CH.sub.3)COOCH.sub.3                              3.067   F     Br      COSCH(CH.sub.3)COOC.sub.2 H.sub.5                       3.068   F     Br      COSCH.sub.2 COOCH(CH.sub.3).sub.2                       3.069   F     Br      COSCH(CH.sub.3)COOCH.sub.2 CHCH.sub.2                   3.070   F     Br      COSCH(CH.sub.3)COOcyclohexyl                            ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                         ##STR16##                                                                    No.   Q     T     Z                                                           ______________________________________                                        4.001 F     Cl    OCH.sub.2 COOH                                              4.002 F     Cl    OCH.sub.2 COOCH.sub.3                                       4.003 F     Cl    OCH.sub.2 COOC.sub.2 H.sub.5                                4.004 F     Cl    OCH.sub.2 COOC.sub.3 H.sub.7 -n                             4.005 F     Cl    OCH.sub.2 COOCH(CH.sub.3).sub.2                             4.006 F     Cl    OCH.sub.2 COOC.sub.4 H.sub.9 -n                             4.007 F     Cl    OCH.sub.2 COOCH.sub.2 CH(CH.sub.3).sub.2                    4.008 F     Cl    OCH.sub.2 COOCH.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5           4.009 F     Cl    OCH.sub.2 COOC(CH.sub.3).sub.3                              4.010 F     Cl    OCH.sub.2 COOcyclohexyl                                     4.011 F     Cl    OCH.sub.2 COOcyclopentyl                                    4.012 F     Cl    OCH.sub.2 COOCH.sub.2 CHCH.sub.2                            4.013 G     Cl    OCH.sub.2 COOCH.sub.2 CCH                                   4.014 F     Cl    OCH.sub.2 COOCH.sub.2 CH.sub.2 Cl                           4.015 F     Cl    OCH.sub.2 COOCH.sub.2 CH.sub.2 OCH.sub.3                    4.016 F     Cl    OCH.sub.2 COOCH.sub.2 CClCH.sub.2                           4.017 F     Cl    OCH(CH.sub.3)COOH                                           4.018 F     Cl    OCH(CH.sub.3)COOCH.sub.3                                                                          m.p.                                                                          185-186°                         4.019 F     Cl    OCH(CH.sub.3)COOC.sub.2 H.sub.5                             4.020 F     Cl    OCH(CH.sub.3)COOC.sub.3 H.sub.7 -n                          4.021 F     Cl    OCH(CH.sub.3)COOCH(CH.sub.3).sub.2                          4.022 F     Cl    OCH(CH.sub.3)COOC.sub.4 H.sub.9 -n                          4.023 F     Cl    OCH(CH.sub.3)COOCH.sub.2 CH(CH.sub.3).sub.2                 4.024 F     Cl    OCH(CH.sub.3)COOCH.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5        4.025 F     Cl    OCH(CH.sub.3)COOC(CH.sub.3).sub.3                           4.026 F     Cl    OCH(CH.sub.3)COOcyclohexyl                                  4.027 F     Cl    OCH(CH.sub.3)COOcyclopentyl                                 4.028 F     Cl    OCH(CH.sub.3)COOCH.sub.2 CHCH.sub.2                         4.029 F     Cl    OCH(CH.sub.3)COOCH.sub.2 CCH                                4.030 F     Cl    OCH(CH.sub.3)COOCH.sub.2 CH.sub.2 Cl                        4.031 F     Cl    OCH(CH.sub.3)COOCH.sub.2 CH.sub.2 OCH.sub.3                 4.032 F     Cl    OCH(CH.sub.3)COOCH.sub.2 CClCH.sub.2                        4.033 F     Br    OCH.sub.2 COOH                                              4.034 F     Br    OCH.sub.2 COOCH.sub.3                                       4.035 F     Br    OCH.sub.2 COOC.sub.2 H.sub.5                                4.036 F     Br    OCH.sub.2 COOCH(CH.sub.3).sub.2                             4.037 F     Br    OCH.sub.2 COOC.sub.4 H.sub.9 -n                             4.038 F     Br    OCH.sub.2 COOCH.sub.2 CHCH.sub.2                            4.039 F     Br    OCH(CH.sub.3)COOH                                           4.040 F     Br    OCH(CH.sub.3)COOCH.sub.3                                    4.041 F     Br    OCH(CH.sub.3)COOC.sub.2 H.sub.5                             4.042 F     Br    OCH(CH.sub.3)COOCH(CH.sub.3).sub.2                          4.043 F     Br    OCH(CH.sub.3)COOC.sub.4 H.sub.9 -n                          4.044 F     Br    OCH(CH.sub.3)COOCH.sub.2 CHCH.sub.2                         4.045 F     Br    OCH(CH.sub.3)COOcyclopentyl                                 4.046 F     Br    OCH(C.sub.2 H.sub.5)COOH                                    4.047 F     Br    OCH(C.sub.2 H.sub.5)COOCH.sub.3                             4.048 F     Br    OCH(C.sub.2 H.sub.5)COOC.sub.2 H.sub.5                      4.049 F     Br    OCH(C.sub.2 H.sub.5)COOCH(CH.sub.3).sub.2                   4.050 F     Br    OCH(C.sub.2 H.sub.5)COOC.sub.4 H.sub.9 -n                   4.051 F     Br    OCH(C.sub.2 H.sub.5)COOCH.sub.2 CHCH.sub.2                  4.052 F     Br    OCH(C.sub.2 H.sub.5)COOcyclohexyl                           ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                         ##STR17##                                                                    No.   Q     T     Z                                                           ______________________________________                                        5.001 F     Cl    SCH.sub.2 COOH                                              5.002 F     Cl    SCH.sub.2 COOCH.sub.3                                       5.003 F     Cl    SCH.sub.2 COOC.sub.2 H.sub.5                                                                     m.p. 101° d.                      5.004 F     Cl    SCH.sub.2 COOC.sub.3 H.sub.7 -n                             5.005 F     Cl    SCH.sub.2 COOCH(CH.sub.3).sub.2                             5.006 F     Cl    SCH.sub.2 COOC.sub.4 H.sub.9 -n                             5.007 F     Cl    SCH.sub.2 COOCH.sub.2 CH(CH.sub.3).sub.2                    5.008 F     Cl    SCH.sub.2 COOCH.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5           5.009 F     Cl    SCH.sub.2 COOC(CH.sub.3).sub.3                              5.010 F     Cl    SCH.sub.2 COOcyclohexyl                                     5.011 F     Cl    SCH.sub.2 COOcyclopentyl                                    5.012 F     Cl    SCH.sub.2 COOCH.sub.2 CHCH.sub.2                            5.013 F     Cl    SCH.sub.2 COOCH.sub.2 CCH                                   5.014 F     Cl    SCH.sub.2 COOCH.sub.2 CH.sub.2 Cl                           5.015 F     Cl    SCH.sub.2 COOCH.sub.2 CH.sub.2 OCH.sub.3                    5.016 F     Cl    SCH.sub.2 COOCH.sub.2 CClCH.sub.2                           5.017 F     Cl    SCH(CH.sub.3)COOH                                           5.018 F     Cl    SCH(CH.sub.3)COOCH.sub.3                                    5.019 F     Cl    SCH(CH.sub.3)COOC.sub.2 H.sub.5                             5.020 F     Cl    SCH(CH.sub.3)COOC.sub.3 H.sub.7 -n                          5.021 F     Cl    SCH(CH.sub.3)COOCH(CH.sub.3).sub.2                          5.022 F     Cl    SCH(CH.sub.3)COOC.sub.4 H.sub.9 -n                          5.023 F     Cl    SCH(CH.sub.3)COOCH.sub.2 CH(CH.sub.3).sub.2                 5.024 F     Cl    SCH(CH.sub.3)COOCH.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5        5.025 F     Cl    SCH(CH.sub.3)COOC(CH.sub.3).sub.3                           5.026 F     Cl    SCH(CH.sub.3)COOcyclohexyl                                  5.027 F     Cl    SCH(CH.sub.3)COOcyclopentyl                                 5.028 F     Cl    SCH(CH.sub.3)COOCH.sub.2 CHCH.sub.2                         5.029 F     Cl    SCH(CH.sub.3)COOCH.sub.2 CCH                                5.030 F     Cl    SCH(CH.sub.3)COOCH.sub.2 CH.sub.2 Cl                        5.031 F     Cl    SCH(CH.sub. 3)COOCH.sub.2 CH.sub.2 OCH.sub.3                5.032 F     Cl    SCH(CH.sub.3)COOCH.sub.2 CClCH.sub.2                        5.033 F     Br    SCH.sub.2 COOH                                              5.034 F     Br    SCH.sub.2 COOCH.sub.3                                       5.035 F     Br    SCH.sub.2 COOC.sub.2 H.sub.5                                5.036 F     Br    SCH.sub.2 COOCH(CH.sub.3).sub.2                             5.037 F     Br    SCH.sub.2 COOC.sub.4 H.sub.9 -n                             5.038 F     Br    SCH.sub.2 COOCH.sub.2 CHCH.sub.2                            5.039 F     Br    SCH(CH.sub.3)COOH                                           5.040 F     Br    SCH(CH.sub.3)COOCH.sub.3                                    5.041 F     Br    SCH(CH.sub.3)COOC.sub.2 H.sub.5                             5.042 F     Br    SCH(CH.sub.3)COOCH(CH.sub.3).sub.2                          5.043 F     Br    SCH(CH.sub.3)COOC.sub.4 H.sub.9 -n                          5.044 F     Br    SCH(CH.sub.3)COOCH.sub.2 CHCH.sub.2                         5.045 F     Br    SCH(CH.sub.3)COOcyclopentyl                                 5.046 F     Br    SCH(C.sub.2 H.sub.5)COOH                                    5.047 F     Br    SCH(C.sub.2 H.sub.5)COOCH.sub.3                             5.048 F     Br    SCH(C.sub.2 H.sub.5)COOC.sub.2 H.sub.5                      5.049 F     Br    SCH(C.sub.2 H.sub.5)COOCH(CH.sub.3).sub.2                   5.050 F     Br    SCH(C.sub.2 H.sub.5)COOC.sub.4 H.sub.9 -n                   5.051 F     Br    SCH(C.sub.2 H.sub.5)COOCH.sub.2 CHCH.sub.2                  5.052 F     Br    SCH(C.sub.2 H.sub.5)COOcyclohexyl                           ______________________________________                                    

FORMULATION EXAMPLES Example 5

Formulation Examples for active ingredients of the formula I (%=per centby weight)

    ______________________________________                                        (a) Wettable powders                                                                             (a)      (b)     (c)                                       ______________________________________                                        active ingredient according                                                                      20%      60%       0.5%                                    to Tables 1 to 5                                                              sodium lignin sulfonate                                                                          5%       5%      5%                                        sodium lauryl sulfate                                                                            3%       --      --                                        sodium diisobutylnaphthalene                                                                     --       6%      6%                                        sulfonate                                                                     octylphenolpolyethylene glycol                                                                   --       2%      2%                                        ether (7-8 mols of ethylene oxide)                                            highly dispersed silicic acid                                                                    5%       27%     27%                                       kaolin             67%      --      --                                        sodium chloride    --       --       59.5%                                    ______________________________________                                    

The active ingredient is well mixed with the additives and the mixtureis ground in a suitable mill. These are thus obtained wettable powderswhich can be diluted with water to give suspensions of the concentrationrequired.

    ______________________________________                                        (b) Emulsion concentrates                                                                            (a)    (b)                                             ______________________________________                                        active ingredient according                                                                          10%    1%                                              to Tables 1 to 5                                                              octylphenolpolyethylene glycol ether                                                                  3%    3%                                              (4-5 mols of ethylene oxide)                                                  calcium dodecyl benzene sulfonate                                                                     3%    3%                                              castor oil polyglycol ether                                                                           4%    4%                                              (36 mols of ethylene oxide)                                                   cyclohexanone          30%    10%                                             xylene mixture         50%    79%                                             ______________________________________                                    

Emulsions of the concentrations required can be obtained from theseconcentrates by diluted with water.

    ______________________________________                                        (c) Dusts            (a)     (b)                                              ______________________________________                                        active ingredient according                                                                        0.1%     1%                                              to Tables 1 to 5                                                              talcum               99.9%   --                                               kaolin               --      99%                                              ______________________________________                                    

Dusts ready for use are obtained by mixing the active ingredient withthe carriers, and grinding the mixture in a suitable mill.

    ______________________________________                                        (d) Extruder granulates                                                                            (a)    (b)                                               ______________________________________                                        active ingredient according                                                                        10%    1%                                                to Tables 1 to 5                                                              sodium lignin sulfonate                                                                             2%    2%                                                carboxymethylcellulose                                                                              1%    1%                                                kaolin               87%    96%                                               ______________________________________                                    

The active ingredient is mixed with the additives, and the mixture isthen ground and moistened with water. It is extruded and subsequentlydried in a stream of air.

    ______________________________________                                        (e) Coated granulate                                                          ______________________________________                                        active ingredient according                                                                         3%                                                      to Tables 1 to 5                                                              polyethylene glycol (M.W. 200)                                                                      3%                                                      kaolin                94%                                                     ______________________________________                                    

The finely ground active ingredient is uniformly applied in a mixer tothe kaolin moistened with polyethylene glycol. Non-dusty coatedgranulates are obtained in this manner.

    ______________________________________                                        (f) Suspension concentrates                                                                         (a)      (b)                                            ______________________________________                                        active ingredient according                                                                         40%      5%                                             to Tables 1 to 5                                                              ethylene glycol       10%      10%                                            nonylphenolpolyethylene glycol                                                                       6%      1%                                             ether (15 mols of ethylene oxide)                                             sodium lignin sulfonate                                                                             10%      5%                                             carboxymethylcellulose                                                                               1%      1%                                             37% aqueous formaldehyde solution                                                                     0.2%     0.2%                                         silicone oil in the form of a                                                                         0.8%     0.8%                                         75% aqueous emulsion                                                          water                 32%      77%                                            ______________________________________                                    

The finely ground active ingredient is intimately mixed with theadditives. There is thus obtained a suspension concentrate from whichcan be produced, by dilution with water, suspensions of theconcentration required.

    ______________________________________                                        (g) Salt solution                                                             ______________________________________                                        active ingredient according                                                                          5%                                                     to Tables 1 to 5                                                              isopropylamine         1%                                                     octylphenolpolyethylene glycol ether                                                                 3%                                                     (78 mols of ethylene oxide)                                                   water                  91%                                                    ______________________________________                                    

BIOLOGICAL EXAMPLES Example 6: Pre-emergence herbicidal action

Immediately after the sowing of the test plants in trays in agreenhouse, the surface of the soil is sprayed with an aqueousdispersion of the active ingredient, the dispersion having been obtainedfrom a 25% emulsion concentrate. Concentrations corresponding to 4 kg ofactive ingredient per hectare are used. The seed trays are kept in agreenhouse at 22°-25° C. with 50-70% relative humidity; the test isconcluded after 3 weeks and the results are then assessed on the basisof the following scale of ratings:

1=plant has not germinated or has died,

2-3=very severe damage,

4=severe damage,

5=moderate damage, the plants have become stunted,

6=damage, but the plant can regenerate,

7-8=slight damage,

9=normal growth, as in the case of the untreated plants.

The results are summarised below.

The compound A is the9-(2,5-diethoxyphenyl)-8,10-dioxo-4,1,7,9-thiatriazabicyclo[5.3.0]decane-4,4-dioxideknown from the German Offenlegungsschrift No. 2,638,543.

    ______________________________________                                                   Avena   Sinapis    Setaria                                                                             Sellaria                                  Compound   sativa  alba       italica                                                                             media                                     ______________________________________                                        1.001      1       1          1     1                                         A          9       9          9     9                                         ______________________________________                                    

Example 7: Post-emergence herbicidal action (contact herbicide)

A number of weeds, both monocotyledonous and dicotyledonous, are sprayedafter emergence (in the 4- to 6-leaf stage) with an aqueousactive-ingredient dispersion at a dosage level corresponding to 4 kg ofactive ingredient per hectare, and the treated plants are kept at24°-26° C. with 45-60% relative humidity. Fifteen days after thetreatment, the test results are evaluated on the basis of the abovescale of ratings. These results are summarised below.

    ______________________________________                                        Plant            Compound 1.001                                                                             A                                               ______________________________________                                        Avena fatua      1            9                                               Setaria italica  1            9                                               Lolium perenne   1            9                                               Sotanum lycopers.                                                                              1            9                                               Sinapis alba     1            7                                               Stellaria media  2            9                                               Phaseolus vulgaris                                                                             1            8                                               ______________________________________                                    

Example 8: Herbicidal action before emergence of the plants

Plastics pots are filled with expanded vermiculite (density: 0.135g/cm³, water-absorption capacity: 0.565 l/l). After saturation of thenon-adsorptive vermiculite with an aqueous active-ingredient emulsion indeionised water, which contains the active ingredient at a concentrationof 70.8 ppm, seeds of the following plants are sown on the surface:Nasturtium officinalis, Agrostis tenuis, Stellaria media and Digitariasanguinalis. The test vessels are subsequently kept in a climaticchamber at 20° C., with an illumination of about 20 k lux and a relativehumidity of 70%. During the germination phase of 4 to 6 days, the potsare covered over with a light-permeable material in order to raise thelocal air humidity and watered with deionised water. After the 5th day,0.5% of a commercial liquid fertiliser (® Greenzit) is added to thewater. The test is evaluated 12 days after sowing, and the effect on thetest plants is assessed.

The tested compounds of the Tables 1 to 5 exhibit in this test a good tovery good herbicidal action.

Example 9: Herbicidal action in the case of paddy rice

The water weeds Echinochloa crus galli and Monocharia vag. are sown inplastic containers (60 cm² surface area, 500 ml volume). After thesowing of the seeds, water is added until it is up to the level of thesoil; and three days after sowing, the level of water is raised toslightly above the soil level (3-5 mm). Application of an aqueousemulsion of the test substance is made, by spraying of the containers,three days after sowing. The applied dose corresponds to anactive-substance amount of 0.5 to 4 kg per hectare (amount of sprayliquor=550 liters per hectare). The plant containers are then kept in agreenhouse under optimum growth conditions for the rice weeds, that is,at 25°-30° C. with high relative humidity. The assessment of the testresults is made three weeks after application of the test substance.

The compounds listed in Tables 1 to 5 attack and destroy the weeds butnot the rice.

Example 10: Reduction in growth of tropical leguminous cover crops

The test plants (Centrosema plumieri and Centrosema pubescens) arecultivated to the fully grown stage, and are then cut back to a heightof 60 cm. After seven days, the active ingredient is sprayed on in theform of an aqueous emulsion. The test plants are maintained at 70%relative humidity and with 6000 lux of artificial light, 14 hours perday, at a temperature of 27° C. by day and 21° C. by night. The testresults are assessed 4 weeks after application of the emulsion. The newgrowth occurring compared with that on the control plants is estimatedand weighed, and the phytotoxicity is evaluated. The plants treated withthe active ingredients from Tables 1 to 5, in an applied amount of50-3000 g per hectare, show in this test a clear reduction in new growth(less than 20% of the new growth occurring on untreated control plants),without the test plants having suffered damage.

Example 11: Regulation of the growth of soya beans

Soya beans of the "Hark" variety are sown in a soil/peat/sand mixture(6:3:1) in plastics containers and these are placed in acontrolled-atmosphere chamber. By virtue of optimum choice oftemperature, illumination, supply of fertiliser and watering, the plantsare able to develop during about five weeks to the 5-6 trifoliateleaf-stage. The plants at this point of time are sprayed with theaqueous spray liquor of an active ingredient of the formula I until theyare fully wetted. The active-ingredient concentration is up to 100 g ofactive ingredient per hectare. An evaluation is made about five weeksafter application of the spray liquor.

The active substances in Tables 1 to 5 effect a marked increase in thenumber and weight of the pods in the leading shoots compared with thosemeasured on the untreated control plants.

Example 12: Reduction in the growth of cereals

The cereal varieties Hordeum vulgare (spring barley) and Secale (springrye) are sown in plastics pots containing sterilised soil in agreenhouse, and watered as required. The young shoots are sprayed, about21 days after sowing, with the aqueous spray liquor of an activeingredient from Tables 1 to 5. The amount of active ingredient isequivalent to up to 100 g per hectare. An assessment of the growth ofthe cereals is made 21 days after application.

The treated plants show a reduction of new growth (60-90% of that ofcontrol plants), and also in some cases an increase in the diameter ofthe stalks.

Example 13: Reduction in the growth of grasses

The grasses Lolium perenne, Poa pratensis, Festuca ovina, Dactylisglomerate and Cynodon dactylon are sown, in a greenhouse, in plasticsdishes containing a soil/peat/sand mixture (6:3:1), and watered asrequired. The emerged grasses are cut back weekly to a height of about 4cm, and are sprayed, about 50 days after sowing and one day after thefinal cutting, with the aqueous spray liquor of an active ingredientfrom Tables 1 to 5. The amount of active ingredient corresponds, whenconverted, to up to 500 g per hectare. The growth of the grasses isassessed 21 days after application of the spray liquor.

The tested compounds of Tables 1 to 5 effect a reduction on new growthof around 10-30% compared with the new growth on the control plants.

Example 14: Desiccating and defoliating action

Cotton plants of the Deltapine variety are grown in clay pots in agreenhouse. After the bolls have finished forming, the plants aresprayed with aqueous preparations of the active ingredient in amountsequivalent to 1.2, 0.6 and 0.3 kg per hectare in the field. Untreatedplants are used as control specimens. An evaluation of the test is made3, 7 and 14 days after application of the test substance by determiningthe degree of defoliation (% of leaves which have fallen) and ofdesiccation (% drying out of the leaves remaining on the plant).

In this test, the compounds of Tables 1 to 5 in applied amounts of 0.6and 1.2 kg/hectare, respectively, left after 7 days just a very fewdried up leaves on the plants (more than 80% leaf-fall and desiccation).

What is claimed is:
 1. An annularly-linked triazole compound of theformula I ##STR18## wherein Q is fluorine,T is chlorine or bromine, Z isa radical --XR, X is oxygen or sulfur, R is a C₂ -C₆ -alkenyl or C₃ -C₆-alkynyl radical, which is unsubstituted or substituted by halogen, oris a radical --A--COXR₁, in which A is a C₁ -C₄ -alkylene bridge and R₁is C₁ -C₄ -alkyl.
 2. A compound according to claim 1 of the formula IwhereinX is oxygen, R is a C₂ -C₆ -alkenyl or C₃ -C₆ -alkynyl radical,which is unsubstituted or substituted by halogen.
 3. A compoundaccording to claim 1 of the formula I whereinR is a radical --A--COXR₁.4.9-(2-Fluoro-4-chloro-5-propynyloxyphenyl)-8,10-dioxo-4,1,7,9-thiatriazabicyclo[5.3.0]decane-4,4-dioxideaccording to claim
 1. 5.9-[2-Fluoro-4-chloro-5-(2'-chloroallyloxy)phenyl]-8,10-dioxo-4,1,7,9-thiatraizabicyclo[5.3.0]-decane-4,4-dioxideaccording to claim
 1. 6.9-[2-Fluoro-4-chloro-5-(1',2'-dichlorovinyl)phenyl]-8,10-dioxo-4,1,7,9-thiatriazabicyclo[5.3.0]decane-4,4-dioxideaccording to claim
 1. 7.9-[2-Fluoro-4-chloro-5-(methoxycarbonyleth-1-yloxy)phenyl]-8,10-dioxo-4,1,7,9-thiatriazabicyclo[5.3.0]decane-4,4-dioxideaccording to claim
 1. 8.9-[2-Fluoro-4-chloro-5-(ethoxycarbonylmethylthio)phenyl]-8,10-dioxo-4,1,7,9-thiatriazabicyclo[5.3.0]decane-4,4-dioxideaccording to claim
 1. 9. A herbicidal and plant-growth regulatingcomposition which contains as active ingredient an effective amount ofan annularly-linked triazole compound according to claim 1, togetherwith inert carriers and/or other additives.
 10. A method of selectivelycontrolling, before or after emergence of the plants, weeds in crops ofcereals, maize, rice and rape-seed, which method comprises treating saidcrops or the cultivated area thereof with a herbicidally effectiveamount of an active substance according to claim 1, or of a compositioncontaining such a compound as active ingredient.
 11. A method ofsuppressing plant growth beyond the 2-leaf stage, which method comprisestreating the plants during their growth with a growth regulatinglyeffective amount of an active substance according to claim 1, or of acomposition containing such a compound as active ingredient.